CN113508033B

CN113508033B - Conductive laminate, touch panel, and method for producing conductive laminate

Info

Publication number: CN113508033B
Application number: CN202080017349.XA
Authority: CN
Inventors: 井上大辅
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2019-03-26
Filing date: 2020-02-19
Publication date: 2023-05-23
Anticipated expiration: 2040-02-19
Also published as: JP2023181466A; CN113508033A; WO2020195370A1; JPWO2020195370A1; US20210389834A1; JP7381562B2

Abstract

The invention provides a conductive laminate, a touch panel, and a method for manufacturing the conductive laminate, wherein breakage of a thin metal wire is suppressed when the laminate is left standing in a high-temperature environment. The conductive laminate comprises: a 1 st organic film; a metal thin wire disposed on the 1 st organic film; and a 2 nd organic film disposed so as to cover the thin metal wire, the thin metal wire including a blackened layer, an adhesive layer, and a metal conductive layer in this order from the 1 st organic film side, the 1 st organic film and the 2 nd organic film having a water content of less than 3.00%.

Description

Conductive laminate, touch panel, and method for producing conductive laminate

Technical Field

The invention relates to a conductive laminate, a touch panel, and a method for manufacturing the conductive laminate.

Background

Conductive substrates having thin metal wires are widely used for various applications such as touch panels, solar cells, and EL (electroluminescence) elements. In particular, in recent years, the mounting rate of touch panels in mobile phones and portable game devices has increased, and there has been a rapid increase in demand for conductive substrates for touch panels of electrostatic capacitance type capable of multi-point detection.

For example, patent document 1 discloses a touch panel sensor in which a blackened layer and copper wiring are disposed on a substrate.

Technical literature of the prior art

Patent literature

Patent document 1: japanese patent application laid-open No. 2013-206315

Disclosure of Invention

Technical problem to be solved by the invention

In general, an organic film may be disposed so as to cover the thin metal wires disposed on the organic film for the purpose of protecting the thin metal wires.

The inventors of the present invention studied the characteristics of a conductive laminate obtained by disposing an adhesive layer between a blackened layer and a metal conductive layer in order to improve the adhesion between the blackened layer and the metal conductive layer and disposing an organic film on the obtained metal fine wire, and found that when the conductive laminate is left to stand under a high-temperature environment, breakage of the metal fine wire may occur. The broken wire of the metal thin wire does not depend on the width of the thin wire.

In view of the above-described circumstances, an object of the present invention is to provide a conductive laminate in which breakage of a fine metal wire is suppressed when the laminate is left standing in a high-temperature environment.

The present invention also provides a method for manufacturing a touch panel and a conductive laminate.

Means for solving the technical problems

The present inventors have made intensive studies on the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by the following constitution.

(1) A conductive laminate, comprising:

a 1 st organic film;

a metal thin wire disposed on the 1 st organic film; a kind of electronic device with high-pressure air-conditioning system

The 2 nd organic film is disposed so as to cover the thin metal wire,

the metal thin wire comprises a blackening layer, an adhesion layer and a metal conductive layer from the 1 st organic film side,

the water content of the 1 st organic film and the 2 nd organic film is less than 3.00%.

(2) The conductive laminate according to (1), wherein the water content is less than 1.00%.

(3) The conductive laminate according to (1) or (2), wherein the blackened layer and the adhesive layer contain the same metal atom.

(4) The conductive laminate according to any one of (1) to (3), wherein the 1 st organic film and the 2 nd organic film are composed of the same material.

(5) The conductive laminate according to any one of (1) to (4), wherein the line width of the fine metal line becomes gradually smaller from the 1 st organic film side toward the 2 nd organic film side.

(6) The conductive laminate according to any one of (1) to (5), wherein an inorganic film is disposed between the fine metal wire and the 2 nd organic film so as to cover the fine metal wire, the inorganic film comprising: at least one metal atom selected from the group consisting of Si, al and Ti.

(7) The conductive laminate according to (6), wherein the inorganic film comprises: selected from the group consisting of SiO ₂ 、SiON、SiN、Al ₂ O ₃ TiO (titanium dioxide) ₂ At least one of the group of (c).

(8) The conductive laminate according to any one of (1) to (7), wherein the metal conductive layer comprises: at least one metal atom selected from the group consisting of Cu, al and Ag.

(9) The conductive laminate according to any one of (1) to (8), wherein the blackened layer comprises: at least one metal atom selected from the group consisting of Mo, nb, cr, ti and W.

(10) The conductive laminate according to any one of (1) to (9), wherein the conductive laminate further comprises a support on the opposite side of the 1 st organic film from the 2 nd organic film side.

(11) The conductive laminate according to (10), wherein the support is a glass substrate.

(12) A touch panel comprising the conductive laminate according to any one of (1) to (11).

(13) A method for producing a conductive laminate, comprising:

a step of forming a 1 st organic film;

a step of forming a fine metal wire on the 1 st organic film; a kind of electronic device with high-pressure air-conditioning system

A step of forming a 2 nd organic film so as to cover the thin metal wires,

Effects of the invention

According to the present invention, it is possible to provide a conductive laminate in which breakage of a thin metal wire is suppressed when the laminate is left standing in a high-temperature environment.

Further, according to the present invention, a method for manufacturing a touch panel and a conductive laminate can be provided.

Drawings

Fig. 1 is a cross-sectional view of embodiment 1 of a conductive laminate.

Fig. 2 is a partial plan view showing a grid pattern formed of intersecting thin metal wires.

Fig. 3 is a cross-sectional view of embodiment 2 of the conductive laminate.

Fig. 4 is a cross-sectional view of embodiment 3 of the conductive laminate.

Fig. 5 is a schematic view of a metal wiring pattern formed in the embodiment.

Fig. 6 is a schematic view of a metal wiring pattern formed in the embodiment.

Fig. 7 is a schematic view of a metal wiring pattern formed in the embodiment.

Detailed Description

Hereinafter, preferred embodiments of the present invention will be described.

In the present specification, the numerical range indicated by "to" refers to a range in which numerical values before and after "to" are included as a lower limit value and an upper limit value.

In the present specification, the "organic film" (1 st to 3 rd organic films described later) means a film containing carbon atoms, and may contain heteroatoms (for example, silicon atoms, nitrogen atoms, oxygen atoms, and the like) other than carbon atoms.

As a characteristic point of the conductive laminate of the present invention, there is a point that an organic film having a low water content is used. In the present invention, by surrounding the thin metal wire including the adhesion layer and the metal conductive layer with the organic film having a low water content, peeling of the adhesion layer and the metal conductive layer is suppressed, and disconnection is suppressed.

Embodiment 1

Embodiment 1 of the conductive laminate of the present invention will be described below with reference to the drawings. Fig. 1 shows a cross-sectional view of embodiment 1 of the conductive laminate of the present invention.

The conductive laminate 10A includes the 1 st organic film 12, the fine metal wires 14A, and the 2 nd organic film 16. The thin metal wire 14A includes a blackened layer 20, an adhesive layer 22, and a metal conductive layer 24 in this order from the 1 st organic film 12 side. The thin metal wire 14A disposed on the 1 st organic film 12 is covered with the 2 nd organic film 16. That is, the thin metal wire 14A is surrounded by the 1 st organic film 12 and the 2 nd organic film 16. When the conductive laminate 10A is applied to a touch panel, the conductive laminate 10A is preferably disposed in the touch panel such that the blackened layer 20 of the thin metal wires 14A is disposed on the viewing side of the conductive metal layer 24.

Hereinafter, each component included in the conductive laminate 10A will be described in detail.

(1 st organic film)

The 1 st organic film is one of the members for supporting the thin metal wires.

The water content of the 1 st organic film is less than 3.00%. In view of further suppressing breakage of the thin metal wires when the conductive laminate is left standing in a high-temperature environment (hereinafter, also simply referred to as "the excellent effect of the present invention"), the amount of breakage is preferably less than 1.00%, more preferably 0.40% or less. The lower limit is not particularly limited, but 0.001% or more is often the case.

The method for measuring the water content includes the following methods: the object to be measured was conditioned for 24 hours at a temperature of 25℃and a humidity of 50%, and the water content was measured by the Karl Fischer method (150 ℃ C., gasification method).

In the present specification, "karl fischer-tropsch (150 ℃ C., gasification method)" means that the moisture content is measured by a moisture gasification method at a gasification temperature of 150 ℃ using a karl fischer-tropsch moisture meter according to JIS K0113.

The thickness of the 1 st organic film is not particularly limited, but from the viewpoint of more excellent effect of the present invention, preferably 0.5 to 5.0. Mu.m, more preferably 1.0 to 3.0. Mu.m.

The material constituting the 1 st organic film is not particularly limited as long as it satisfies the above water content, and a resin is preferable. For example, (meth) acrylic resins, polystyrene resins, polyolefin resins, fluorine resins, polyimide resins, fluorinated polyimide resins, polyurethane resins, polyether ether ketone resins, polycarbonate resins, and silicon-containing resins are mentioned, and (meth) acrylic resins or silicon-containing resins are preferable.

The term "meth" refers to a written language including both an acrylic resin and a methacrylic resin.

The silicon-containing resin means an organic resin containing silicon atoms. Examples of the silicon-containing resin include polysilazane having an organic group and an organic resin having a silsesquioxane structure.

From the viewpoint of the water content in the organic film becoming lower, the (meth) acrylic resin preferably has a carbocycle. Examples of the carbocycle include aliphatic rings such as cyclohexane ring, and aromatic rings such as benzene ring, naphthalene ring, fluorene ring, anthracene ring and phenanthrene ring.

Carbocycles may be monocyclic or heterocyclic.

As the carbocycle, a benzene ring or a fluorene ring is preferable, more preferably a fluorene ring.

Examples of the monomer capable of constituting the repeating unit contained in the (meth) acrylic resin include acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, and methacrylic esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate.

The (meth) acrylic resin may be a homopolymer of one derivative of (meth) acrylic acid, a copolymer of two or more derivatives of (meth) acrylic acid, or a copolymer of these with other monomers copolymerizable with these.

In view of the more excellent effect of the present invention, the weight average molecular weight Mw of the (meth) acrylic resin is preferably 20,000 or more, more preferably 25,000 or more, and preferably 600,000 or less, more preferably 350,000 or less.

The weight average molecular weight (hereinafter abbreviated as Mw) is a value in terms of polystyrene based on Gel Permeation Chromatography (GPC). Specific measurement conditions of GPC include the following measurement conditions.

GPC apparatus: HLC-8320 (TOSOH CORPORATION manufacturing)

Column: and TSK gel SuperHZM-H, TSK gel SuperHZ4000, TSK gel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID (inner diameter). Times.15.0 cm)

Eluent: tetrahydrofuran (THF)

As the (meth) acrylic resin, a (meth) acrylic resin produced by a known method may be used, or a commercially available product may be used. Examples of commercial products include DELPET 60N, 80N (manufactured by Asahi Kasei Chemicals Corporation), dianal BR80, BR83, BR85, BR88, BR95, BR110, and BR113 (manufactured by MITSUBISHI RAYON co., ltd.).

When the material constituting the 1 st organic film is a resin, the resin may have a crosslinked structure.

As a method for forming a resin having a crosslinked structure, a method of curing a polyfunctional monomer to obtain a resin can be mentioned.

The type of the polymerizable group included in the polyfunctional monomer is not particularly limited, and examples thereof include a radical polymerizable group (e.g., a (meth) acryl group) and a cation polymerizable group.

The number of polymerizable groups in the polyfunctional monomer is not particularly limited, but is preferably 2 or more, more preferably 3 to 6.

When a monomer is used in the production of the 1 st organic film, a polymerization initiator may be used in combination as required. The polymerization initiator may be selected as an optimum initiator depending on the polymerization form, and examples thereof include radical polymerization initiators and cationic polymerization initiators.

The method for forming the 1 st organic film is not particularly limited, and a known method can be used. For example, a method of forming a coating film using a composition containing a predetermined monomer and curing the coating film to form a 1 st organic film, a method of applying a composition containing a predetermined resin and, if necessary, drying the composition to form a 1 st organic film, and a method of melting the resin and molding the film into a film are exemplified.

(thin metal wire)

The metal thin line includes a blackened layer, an adhesive layer and a metal conductive layer. The respective layers will be described in detail below.

The blackened layer is a layer for suppressing reflection of light to reduce visibility of the thin metal wire.

The material constituting the blackened layer is not particularly limited, and known materials can be applied. Wherein the blackened layer preferably comprises: at least one metal atom selected from the group consisting of Mo, nb, cr, ti, W, ni, ta, V, fe, co, cu, sn and Mn, more preferably, comprises: at least one metal atom selected from the group consisting of Mo, nb, cr, ti and W.

The blackened layer may contain other atoms (for example, carbon atoms, oxygen atoms, nitrogen atoms, and hydrogen atoms) than the atoms of the above-described metal.

The blackened layer may contain a metal monomer composed of the above metal atoms or a metal alloy composed of two or more metal atoms. The blackening layer may contain an oxide, nitride, or oxynitride of the metal atom.

The thickness of the blackened layer is not particularly limited, but is preferably 1 to 100nm, more preferably 3 to 30nm, from the viewpoint of sufficiently suppressing reflection of light and being excellent in industrial properties.

The adhesion layer is a layer for ensuring adhesion between the blackened layer and the metal conductive layer.

The material constituting the adhesive layer is not particularly limited, and known materials can be applied. Wherein the adhesive layer preferably comprises: at least one metal atom selected from the group consisting of Mo, nb, cr, ti, W, ni, ta, V, fe, co, cu, sn and Mn, more preferably, comprises: at least one metal atom selected from the group consisting of Mo, nb, cr, ti and W.

The adhesion layer may contain other atoms (e.g., carbon atoms, oxygen atoms, nitrogen atoms, and hydrogen atoms) other than the atoms of the above metals.

The adhesive layer may contain a metal monomer composed of the above metal atoms or a metal alloy composed of two or more metal atoms. The adhesion layer may contain an oxide, nitride, or oxynitride of the metal atom.

From the viewpoint that the adhesion of the adhesion layer to the blackened layer becomes better, the blackened layer and the adhesion layer preferably contain the same metal atom.

Further, even if the constituent components of the adhesive layer and the blackened layer are the same, the functions may be different depending on the density. The density of the adhesion layer and the blackening layer may vary depending on the conditions (e.g., sputtering conditions) at the time of formation.

The thickness of the adhesive layer is not particularly limited, but is preferably 1 to 100nm, more preferably 20 to 60nm, from the viewpoint of more excellent effect of the present invention.

The metal conductive layer is a member capable of imparting conductivity to the conductive laminate.

The material constituting the metal conductive layer is not particularly limited, and a known material can be applied. Wherein the metal conductive layer preferably comprises at least one metal atom selected from the group consisting of Cu, al, ag, pt, ni and Pd, more preferably comprises: at least one metal atom selected from the group consisting of Cu, al and Ag.

The metal conductive layer may contain a metal monomer composed of the above metal atoms or a metal alloy composed of two or more metal atoms.

The thickness of the metal conductive layer is not particularly limited, but is preferably 10 to 700nm, more preferably 100 to 600nm, from the viewpoint of conductivity.

The thin metal wire may include layers other than the blackened layer, the adhesive layer, and the metal conductive layer.

For example, the thin metal wire may include an adhesion layer and a protective layer on a surface of the metal conductive layer on a side opposite to the adhesion layer side.

The adhesion layer disposed between the metal conductive layer and the protective layer is a layer for ensuring adhesion of both. The adhesive layer may be formed by the above-described adhesive layer disposed between the blackened layer and the metal conductive layer.

The protective layer is a layer having a function of protecting the metal conductive layer.

The protective layer may have the same structure as the blackened layer.

The shape of the thin metal wire is not particularly limited, but a shape in which the line width of the thin metal wire gradually decreases from the 1 st organic film side toward the 2 nd organic film side is preferable (refer to fig. 1). That is, the thin metal wire preferably has a tapered cross-sectional shape. When the thin metal wire has the above-described shape, the thin metal wire is less easily visually recognized.

The angle (θ1 in fig. 1, hereinafter also referred to as taper angle) formed by the inclined surface of the fine metal wire having a tapered cross-sectional shape and the surface of the 1 st organic film is not particularly limited, but is preferably 60 to 80 °.

The line width of the 1 st organic film side of the blackened layer and the line width of the 1 st organic film side of the metal conductive layer may be different, and the ratio of the line width W2 of the 1 st organic film side of the metal conductive layer to the line width W1 of the 1 st organic film side of the blackened layer { (W2/W1) ×100 (%) } (see fig. 1) is preferably 90 to 99.9%. If the ratio is within the above range, the thin metal wire is less likely to be visually recognized.

The line width of the fine metal line is not particularly limited, but is preferably 30 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, particularly preferably 9 μm or less, most preferably 7 μm or less, and preferably 0.5 μm or more, further preferably 1.0 μm or more. If the amount is within the above range, an electrode having low resistance and being difficult to be visually recognized can be formed.

In addition, the line width of the thin metal lines is the maximum line width among the thin metal lines, and in the case of the thin metal lines having a tapered cross-sectional shape as shown in fig. 1, the line width of the 1 st organic film side of the blackened layer corresponds to the line width of the thin metal lines.

The thickness of the thin metal wire is not particularly limited, but is preferably 0.01 to 20. Mu.m, more preferably 0.01 to 10. Mu.m, and still more preferably 0.01 to 5. Mu.m. If the amount is within the above range, an electrode having low resistance and being difficult to be visually recognized can be formed.

The thin metal wire may be patterned, for example, but not limited to, triangular shapes such as regular triangle, isosceles triangle, and right triangle, quadrilaterals (for example, square, rectangle, diamond, parallelogram, trapezoid, and the like), regular hexagons, (regular) octagons, and the like, (regular) n-sided shapes, circles, ellipses, stars, and geometric figures combining them, and more preferably, a mesh shape (mesh pattern).

The mesh shape may include a shape including a plurality of openings 18 formed by intersecting thin metal wires 14A as shown in fig. 2. The length L of one side of the opening 18 is not particularly limited, but is preferably 1500 μm or less, more preferably 1300 μm or less, further preferably 1000 μm or less, and preferably 5 μm or more, more preferably 30 μm or more, further preferably 80 μm or more.

When the length of one side of the opening is within the above range, the transparency of the conductive laminate becomes more excellent.

In fig. 2, the opening 18 has a diamond shape, but may have other shapes. For example, it may be set to a polygon (e.g., triangle, quadrangle, hexagon, and random polygon). The shape of one side may be curved, or may be circular arc, in addition to linear. When the shape is circular, for example, the opposite sides may be circular protruding outward, and the other opposite sides may be circular protruding inward. The shape of each side may be a wavy line shape in which an arc protruding outward and an arc protruding inward are continuous. Of course, the shape of each side may be sinusoidal.

The aperture ratio of the mesh pattern formed of the fine metal wires is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more from the viewpoint of visible light transmittance. The aperture ratio corresponds to the ratio of the region on the 1 st organic film except the region where the thin metal wire is located to the entire region.

The method for forming the thin metal wire is not particularly limited, and examples thereof include known methods such as sputtering, ion plating, and vapor deposition.

Further, as a method for forming the thin metal wire at a predetermined position, a known method can be mentioned. As an example, the following method may be mentioned: after the blackened layer, the adhesive layer and the metal conductive layer are formed on the entire surface of the 1 st organic film by a sputtering method, a patterned resist film is formed on the metal conductive layer, and the blackened layer, the adhesive layer and the metal conductive layer at the opening of the resist film are removed, whereby the metal thin line is disposed at a predetermined position.

The method for removing the unnecessary layer may be either wet etching (e.g., etching using an etching solution) or dry etching.

(2 nd organic film)

The 2 nd organic film is one of the members for supporting the thin metal wire together with the 1 st organic film.

The constitution of the 2 nd organic film is the same as that of the 1 st organic film. For example, the range of the water content of the 2 nd organic film is the same as the range of the water content of the 1 st organic film.

The thickness of the 2 nd organic film is preferably 0.5 to 5.0 μm, more preferably 1.0 to 3.0 μm, from the viewpoint of covering the fine metal wires and smoothing the surface of the 2 nd organic film.

The preferable mode of the material constituting the 2 nd organic film is the same as the preferable mode of the material constituting the 1 st organic film.

The method for forming the 2 nd organic film is the same as the method for forming the 1 st organic film.

In view of the more excellent effect of the present invention, it is preferable that the 1 st organic film and the 2 nd organic film are composed of the same material. By being composed of the same material, the adhesion of the 1 st organic film and the 2 nd organic film is also improved.

The conductive laminate can be produced by a known method.

Among them, the method is preferably used for manufacturing the semiconductor device having the following steps: a step of forming a 1 st organic film; a step of forming a fine metal wire on the 1 st organic film; and a step of forming a 2 nd organic film so as to cover the thin metal wire.

The specific manufacturing methods of the respective members (organic film 1, thin metal wire, organic film 2) are as described above.

The conductive laminate may include components other than those described above.

For example, a conductive portion other than the thin metal wires (for example, conductive terminal portions disposed at both ends of a mesh pattern formed of the thin metal wires) may be disposed between the 1 st organic film and the 2 nd organic film.

< embodiment 2 >

Embodiment 2 of the conductive laminate of the present invention will be described below with reference to the drawings. Fig. 3 shows a cross-sectional view of embodiment 2 of the conductive laminate of the present invention.

The conductive laminate 10B includes the 1 st organic film 12, the fine metal wires 14A, the inorganic film 26, and the 2 nd organic film 16. The thin metal wire 14A includes a blackened layer 20, an adhesive layer 22, and a metal conductive layer 24 in this order from the 1 st organic film 12 side.

The conductive laminate 10B has the same configuration as the conductive laminate 10A except for the inorganic film 26, and therefore the same reference numerals are given to the same constituent elements, and the description thereof is omitted.

The inorganic film 26 will be described in detail below.

(inorganic film)

The inorganic film is a film disposed between the 1 st organic film and the 2 nd organic film so as to cover the thin metal wires. By disposing the inorganic film, the effect of the present invention is more excellent.

The material constituting the inorganic film is not particularly limited, and preferably includes: at least one metal atom selected from the group consisting of Si, al and Ti.

The inorganic film may contain atoms other than the atoms of the above-described metals (for example, carbon atoms, oxygen atoms, nitrogen atoms, and hydrogen atoms).

The inorganic film may contain an oxide, nitride or oxynitride of the above metal atom, and preferably contains: selected from the group consisting of SiO ₂ 、SiON、SiN、Al ₂ O ₃ TiO (titanium dioxide) ₂ At least one of the group of (c).

The thickness of the inorganic film is not particularly limited, but is preferably 10 to 1000nm, more preferably 20 to 200nm.

As shown in fig. 3, the inorganic film may be disposed so as to cover the 1 st organic film and the thin metal wires, or may be disposed so as to cover only the thin metal wires.

The method for forming the inorganic film is not particularly limited, and examples thereof include known methods, such as sputtering, ion plating, chemical Vapor Deposition (CVD), and liquid deposition methods such as electroplating and sol-gel methods.

Embodiment 3

Embodiment 3 of the conductive laminate of the present invention will be described below with reference to the drawings. Fig. 4 shows a cross-sectional view of embodiment 3 of the conductive laminate of the present invention.

The conductive laminate 10C includes a support 28, the 1 st organic film 12, the metal thin lines 14A, the 2 nd organic film 16, the metal thin lines 14B, the inorganic film 26, and the 3 rd organic film 30. The

thin metal wires

14A and 14B include a blackened layer 20, an adhesive layer 22, and a metal conductive layer 24 in this order from the 1 st organic film 12 side.

When the conductive laminate 10C is applied to a touch panel, the conductive laminate 10C is preferably disposed in the touch panel so that the blackening layer 20 of the thin metal lines 14A is disposed on the visual side of the conductive metal layer 24. That is, in the touch panel, the support 28 is preferably disposed on the viewing side. In this case, the support 28 may constitute a touch surface in the touch panel.

The 1 st organic film 12, the fine metal wires 14A, and the 2 nd organic film 16 in the conductive laminate 10C correspond to the 1 st organic film 12, the fine metal wires 14A, and the 2 nd organic film 16 in the conductive laminate 10A, respectively, and therefore, the description thereof is omitted.

Hereinafter, the support 28, the fine metal wire 14B (hereinafter also referred to as "the 2 nd fine metal wire"), the inorganic film 26, and the 3 rd organic film 30 included in the conductive laminate 10C will be described in detail.

(support)

The support body is a member for supporting other members. More specifically, the organic film functions as a member in forming the 1 st organic film.

The type of the support is not particularly limited, and examples thereof include a glass substrate and a resin substrate, and a glass substrate is preferable from the viewpoints of transparency and light resistance.

Examples of the material constituting the resin substrate include thermoplastic resins, and examples of the thermoplastic resins include polyester resins such as polyethylene terephthalate, methacrylic resins, methacrylic acid-maleic acid copolymers, polystyrene resins, transparent fluorine resins, polyimides, fluorinated polyimide resins, polyamide resins, polyamideimide resins, polyether imide resins, cellulose acylate resins, polyurethane resins, polyether ether ketone resins, polycarbonate resins, alicyclic polyolefin resins, polyarylate resins, polyether sulfone resins, polysulfone resins, cycloolefin copolymers, fluorene ring-modified polycarbonate resins, alicyclic modified polycarbonate resins, and fluorene ring-modified polyester resins.

The thickness of the support is not particularly limited, and may be 25 to 500. Mu.m.

The total light transmittance of the support is preferably 85 to 100%.

As the support, a temporary support (releasable support) can be used. When the temporary support is used as the support, the member disposed on the temporary support can be transferred to another adherend. In this case, peeling occurs between the temporary support and the 1 st organic film, and the temporary support can be peeled off.

(No. 2 fine metal wire)

The 2 nd metal thin line is a thin line arranged between the 2 nd organic film and the 3 rd organic film.

The constitution of the 2 nd thin metal wire is the same as that of the thin metal wire described in embodiment 1 above.

(inorganic film)

The inorganic film is a film disposed between the 2 nd and 3 rd organic films so as to cover the 2 nd thin metal wire. By disposing the inorganic film, the effect of the present invention is more excellent.

The composition of the inorganic film is the same as that of the inorganic film described in embodiment 2.

(3 rd organic film)

The 3 rd organic film is a film disposed so as to cover the 2 nd thin metal wire.

The 3 rd organic film has the same structure as the 1 st organic film described in embodiment 1. For example, the range of the water content of the 3 rd organic film is the same as the range of the water content of the 1 st organic film.

The preferable range of the thickness of the 3 rd organic film is the same as the preferable range of the thickness of the 1 st organic film.

The preferable mode of the material constituting the 3 rd organic film is the same as the preferable mode of the material constituting the 1 st organic film.

The method for forming the 3 rd organic film is the same as the method for forming the 1 st organic film.

The conductive laminate of the present invention can be preferably used for a touch panel.

The type of the touch panel having the conductive laminate of the present invention is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include a surface type electrostatic capacitance type touch panel, a projected type electrostatic capacitance type touch panel, and a resistive film type touch panel. In addition, the touch panel includes a so-called touch sensor and a touch panel.

The touch panel is suitable for various display devices (such as a liquid crystal display device and an organic electroluminescence display device).

Examples

The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.

Example 1 >

(preparation of support)

The surface of a 10cm square glass substrate (Corning Incorporated co., ltd., EAGLE XG glass) was subjected to UV (ultraviolet) ozone treatment for 5 minutes. Then, the obtained glass substrate was immersed in an aqueous solution in which CLEAN ACE manufactured by AS ONE Corporation was diluted to 30 mass%, and the surface of the glass substrate was scrubbed using BELCLEAN manufactured by AION co. Then, the obtained glass substrate was immersed in pure water, and the surface of the glass substrate was scrubbed using BELCLEAN in the same manner as described above. Then, the obtained glass substrate was blown with air, and dried at 200℃for 30 minutes.

(formation of the 1 st organic film)

Trimethylolpropane triacrylate (manufactured by TOAGOSEI co., ltd.) and a photopolymerization initiator (esaceure KTO46 manufactured by Lamberti s.p.a.) were mixed at 95.5 mass%, and then dissolved in methyl ethyl ketone to a solid content concentration of 10 mass%, to obtain a composition for forming an organic film.

Next, the organic film-forming composition was applied to the glass substrate subjected to the above-described cleaning treatment using an automatic coater PI1210 manufactured by ster SANGYO CO,. Ltd. Using a coating bar (effective width 20 mm), and then dried at 120 ℃ for 3 minutes to form a coating film. The coating speed was set to 100mm/sec.

Next, the coating film was subjected to UV irradiation (600 mJ/cm) at an oxygen concentration of 200 ppm by volume and a temperature of 80℃using a metal halide lamp MAL625NL manufactured by Nippon Denchi Kabushiki Kaisha ² ) Thereby obtaining a cured film. Then, the cured film was dried under vacuum at 80℃for 12 hours to obtain a 1 st organic film (thickness: 1.5 μm).

(formation of No. 1 thin metal wire)

A MoNb film (Mo content: 80% by mass, nb content: 20% by mass) having a film thickness of 10nm was formed on the obtained 1 st organic film by a magnetron sputtering method. As conditions for the magnetron sputtering method, the magnetic field strength was 1000Gauss, the substrate temperature was 30℃and the vacuum degree was 5.0X10 ^-2 Pa, 7kW of power, and 0.8nm/min of film forming speed.

Then, by magnetic sputteringA MoNb film (Mo content: 80 mass% and Nb content: 20 mass%) having a film thickness of 40nm was formed on the MoNb film by the sputtering method. As conditions for the magnetron sputtering method, the magnetic field strength was 1000Gauss, the substrate temperature was 30℃and the vacuum degree was 5.0X10 ^-2 Pa, power of 8kW, film forming speed of 0.6nm/min.

Next, a Cu film with a film thickness of 200nm was formed on the MoNb film by a magnetron sputtering method. As conditions for the magnetron sputtering method, the magnetic field strength was 1000Gauss, the substrate temperature was 30℃and the vacuum degree was 5.0X10 ^-2 Pa, power 5kW, film forming speed 0.4nm/min.

Then, a CuNi film (Cu content: 75 mass% and Ni content: 25 mass%) having a film thickness of 80nm was formed on the Cu film by magnetron sputtering. As conditions for the magnetron sputtering method, the magnetic field strength was 1000Gauss, the substrate temperature was 30℃and the vacuum degree was 5.0X10 ^-2 Pa, power 6kW, film forming speed 0.8nm/min.

Next, a MoNb film (Mo content: 80 mass% and Nb content: 20 mass%) having a film thickness of 100nm was formed on the CuNi film by a magnetron sputtering method. As conditions for the magnetron sputtering method, the magnetic field strength was 1000Gauss, the substrate temperature was 30℃and the vacuum degree was 5.0X10 ^-2 Pa, power 4kW, film forming speed 0.5nm/min.

In the magnetron sputtering method, argon is used as an inert gas.

Next, OAP manufactured by Tokyo Ohka Kogyo co., ltd. Next, as a resist for pattern formation, novolac OFPR800 manufactured by Tokyo Ohka Kogyo co., ltd. The above coating uses MIKASA co., ltd. After the above coating, the film was dried at 90℃for 3 minutes to obtain a resist film having a film thickness of 1. Mu.m.

Next, the resist film was irradiated with light for 10 seconds using a mesh photomask and using a mask aligner MA-20 (mercury light source) manufactured by MIKASA co., ltd. Then, a patterned resist film was obtained by immersing in an aqueous solution of NMD-W2.38% manufactured by Tokyo Ohka Kogyo co., ltd. For 5 minutes, followed by immersing in pure water for 1 minute and drying at 120 ℃ for 3 minutes.

The glass substrate having the patterned resist film was immersed in an etching solution (TOAGOSEI co., ltd. Manufactured: ferric chloride solution) at a temperature of 50 ℃ for 1 minute, then immersed in pure water for 5 minutes, and then blown with air, and dried at 120 ℃ for 3 minutes, to obtain a fine metallic wire in a mesh form as shown in fig. 2.

The formed thin metal wire includes, in order, a MoNb film (blackened layer), a MoNb film (adhered layer), a Cu film (metal conductive layer), a CuNi film (adhered layer), and a MoNb film (protective layer). As shown in fig. 1, the thin metal wire has a tapered cross-sectional shape, the line width of the thin metal wire (line width corresponding to the 1 st organic film side of the blackened layer) is 4.0 μm, the taper angle θ1 is 70 °, and the ratio of the line width W2 of the 1 st organic film side of the metal conductive layer to the line width W1 of the 1 st organic film side of the blackened layer is 97%.

As shown in fig. 5, 20 units 44 are arranged on the 1 st organic film, and each unit 44 is composed of a mesh pattern 40 formed of the 1 st metal thin wire having the mesh shape and 2 resistance value measurement terminals 42 sandwiching the mesh pattern 40. The length of one side of the grid-shaped opening of the grid pattern was 500 μm, and one angle (angle θ2 in fig. 2) of the diamond-shaped opening was 65 °. The size of the resistance value measurement terminal 42 was 2mm×1mm, and the interval between the cells 44 was 2mm.

(formation of No. 2 organic film)

In the same manner as described above (formation of the 1 st organic film), the 2 nd organic film having a thickness of 2.5 μm was formed on the 1 st organic film on which the fine metal wire was formed.

(formation of No. 2 thin metal wire)

The mesh-like 2 nd fine metal wires were formed on the 2 nd organic film in the same manner as the above (1 st fine metal wires). Wherein the mesh-shaped 2 nd metal thin lines are formed such that the intersections of the mesh pattern formed by the 1 st metal thin lines are located at the openings of the mesh pattern formed by the 2 nd metal thin lines.

As shown in fig. 6, 20 units 44 are arranged on the 2 nd organic film, and each unit 44 is composed of a mesh pattern 40 formed of the above-described mesh-like 2 nd metal thin wires and 2 resistance value measurement terminals 42 sandwiching the mesh pattern 40. The size of the resistance value measurement terminal 42 was 2mm×1mm, and the interval between the cells 44 was 2mm. In fig. 5 and 6, the direction of arrangement of the cells is different, and the direction of arrangement of the cells of the 2 nd wire is orthogonal to the direction of arrangement of the cells of the 1 st wire.

(formation of inorganic film)

SiO having a thickness of 50nm was formed on the 2 nd organic film on which the 2 nd thin metal wire was disposed by the plasma CVD method ₂ And (3) a film.

In the plasma CVD method, a silane gas, hydrogen gas, and oxygen gas are used as raw material gases. The flow rate of the silane gas was set to 100sccm, the flow rate of the hydrogen gas was set to 1000sccm, and the flow rate of the oxygen gas was set to 200sccm. The vacuum degree was set at 50Pa, the substrate temperature was set at 30 ℃, the electrode input power was set at 6.5kW, and the film formation rate was set at 10nm/min.

(formation of organic film 3)

In the same procedure as described above (formation of the 1 st organic film), in SiO ₂ A2 nd organic film having a thickness of 2.0 μm was formed on the film.

The conductive laminate 1 shown in fig. 4 was obtained by the above steps. When the conductive laminate 1 is viewed from the top surface, a grid pattern is arranged as shown in fig. 7.

Example 2 >

A conductive laminate 2 was obtained in the same manner as in example 1, except that the production conditions of the layers in the above (formation of the 1 st thin metal wire) were changed as in the following (production condition 2).

The 1 st metal thin wire and the 2 nd metal thin wire in the conductive laminate 2 sequentially include Mo ₂ N film (blackened layer), mo film (adhesive layer), al film (metal conductive layer), mo film (adhesive layer) and Mo ₂ N film (protective layer).

(production condition 2)

Mo having a film thickness of 10nm was formed on the 1 st organic film obtained by the magnetron sputtering method ₂ N film. As conditions for the magnetron sputtering method, the magnetic field strength was 1000Gauss, the substrate temperature was 30℃and the vacuum degree was 5.0X10 ^-2 Pa, power 10kW, film forming speed 0.5nm/min.

Next, mo was deposited by magnetron sputtering ₂ A Mo film having a film thickness of 40nm was formed on the N film. As conditions for the magnetron sputtering method, the magnetic field strength was 1000Gauss, the substrate temperature was 30℃and the vacuum degree was 5.0X10 ^-2 Pa, power of 8kW, film forming speed of 0.6nm/min.

Subsequently, an Al film having a film thickness of 200nm was formed on the Mo film by the magnetron sputtering method. As conditions for the magnetron sputtering method, the magnetic field strength was 1000Gauss, the substrate temperature was 30℃and the vacuum degree was 5.0X10 ^-2 Pa, power 6kW, film forming speed 0.4nm/min.

Next, a Mo film having a film thickness of 80nm was formed on the Al film by the magnetron sputtering method. As conditions for the magnetron sputtering method, the magnetic field strength was 1000Gauss, the substrate temperature was 30℃and the vacuum degree was 5.0X10 ^-2 Pa, power 4kW, film forming speed 0.3nm/min.

Next, mo having a film thickness of 100nm was formed on the Mo film by the magnetron sputtering method ₂ N film. As conditions for the magnetron sputtering method, the magnetic field strength was 1000Gauss, the substrate temperature was 30℃and the vacuum degree was 5.0X10 ^-2 Pa, 7kW of power and 0.4nm/min of film forming speed.

In the magnetron sputtering method, nitrogen gas is used as a reaction gas, and argon gas is used as an inert gas.

Examples 3 to 5 >

Conductive laminates 3 to 5 were obtained in the same manner as in example 1, except that the materials described in table 1 were used instead of trimethylolpropane triacrylate.

Examples 6 to 7 >

Conductive laminates 6 to 7 were obtained in the same manner as in example 1, except that the procedure of the above (formation of the 1 st organic film) was changed as follows.

In addition, in the conductive laminates 6 to 7, the 1 st to 3 rd organic films were formed using the materials described in table 1. The thicknesses of the 1 st to 3 rd organic films of the conductive laminated bodies 6 to 7 are the same as the thicknesses of the 1 st to 3 rd organic films of the conductive laminated body 1.

(formation of the 1 st organic film)

BR113 (manufactured by Mitsubishi Rayon co., ltd.) or BR95 (manufactured by Mitsubishi Rayon co., ltd.) was dissolved in methyl ethyl ketone to have a solid content concentration of 10 mass%, to obtain a composition for forming an organic film.

Next, the organic film-forming composition was applied to the glass substrate subjected to the above-described cleaning treatment using an automatic coater PI1210 manufactured by ster SANGYO CO,. Ltd. Using a coating bar (effective width 20 mm), and then dried at 120 ℃ for 3 minutes to form the 1 st organic film. The coating speed was set to 100mm/sec.

Example 8 >

A conductive laminate 8 was obtained in the same manner as in example 1, except that the step of forming the organic film (1 st) was changed as described below.

In addition, in the conductive laminate 8, the 1 st to 3 rd organic films were each formed using the materials described in table 1. The thickness of the 1 st to 3 rd organic films of the conductive laminate 8 is the same as the thickness of the 1 st to 3 rd organic films of the conductive laminate 1.

(formation of the 1 st organic film)

The glass substrate subjected to the cleaning treatment described above was coated with Silplus HT100 (manufactured by Shin Nittetsu Sumikin Kabushiki kaisha) using an automatic coater PI1210 manufactured by ster SANGYO CO,. Ltd. And using a coating bar (effective width 20 mm), and then dried at 120 ℃ for 3 minutes to form a coating film. The coating speed was set to 100mm/sec.

Next, the coating film was subjected to UV irradiation (1000 mJ/cm ² ) Thereby obtaining a cured film.

Examples 9 to 12 >

Conductive laminates 9 to 12 were obtained in the same manner as in example 1, except that the steps described above (formation of the 1 st organic film) were changed as follows, and the line width of the thin metal lines (line width corresponding to the 1 st organic film side of the blackened layer) and the thickness of the metal conductive layer were changed as shown in table 1.

In addition, in the conductive laminates 9 to 12, the 1 st to 3 rd organic films were formed using the materials described in table 1. The thickness of the 1 st to 3 rd organic films of the conductive laminate 9 is the same as the thickness of the 1 st to 3 rd organic films of the conductive laminate 1.

(formation of the 1 st organic film)

A dibutyl ether solution of perhydrosilazane (AQUARCA NN120-20:AZ Electronic Materials Co, manufactured by Ltd.) containing 5% by mass (solid content) of an amine catalyst (N, N, N ', N' -tetramethyl-1, 6-diaminohexane) (AQUARCA NAX120-20:AZ Electronic Materials Co, manufactured by Ltd.) was mixed to prepare a composition for forming an organic film. The amine catalyst content in the obtained composition for forming an organic film was 1% by mass based on the total solid content.

Next, the organic film-forming composition was applied to the glass substrate subjected to the above-mentioned cleaning treatment by using an automatic coater PI1210 manufactured by ster SANGYO CO,. Ltd. Using a coating bar (effective width 20 mm), and then dried at 120 ℃ for 3 minutes to form a coating film. The coating speed was set to 100mm/sec.

Next, the coating film was subjected to UV irradiation (5000 mJ/cm ² ) Thereby obtaining a cured film. Then, the obtained cured film was dried at 80℃for 12 hours to obtain an organic film No. 1.

Example 13 >

A conductive laminate 13 was obtained in the same manner as in example 9, except that the production conditions of the layers in the above (formation of the 1 st thin metal wire) were changed as described above (production condition 2).

Comparative examples 1 to 3

Conductive laminates C1 to C3 were obtained in the same manner as in example 1, except that the monomers described in table 1 were used instead of trimethylolpropane triacrylate.

In comparative example 3, styrene and a9300 were mixed at a mass ratio of 1:1.

< evaluation >

(evaluation of Water content)

Organic films (thickness: 1.5 μm) were produced on glass supports according to the procedures of examples 1 to 13 and comparative examples 1 to 3 (formation of organic film 1).

The obtained organic film was peeled off from the glass support, allowed to stand at 25℃and 50% humidity for 24 hours, and the water content of the organic film was measured by the Karl Fischer method (150 ℃) using the obtained organic film. In addition, the device used AQV-2100 manufactured by hiramoa Sangyo co., ltd.

The results are summarized in Table 1.

(evaluation of broken wire)

100 conductive laminates of examples and comparative examples were produced.

After the conductive laminate was allowed to stand in an environment of 50 ℃ for 1 week, the probes were brought into contact with the resistance measuring terminal portions located at both ends of each cell, and the resistance value was measured by a resistance measuring machine. Of the total 40 cells in each conductive laminate, if 1 cell was broken, the number of broken lines was counted.

Of the 100 samples to be measured, the number of samples in which disconnection occurred was 10 or more, 1 minute, 3 to 9 were 2 minutes, 1 to 2 were 3 minutes, and 0 was 4 minutes.

Each symbol in the column "materials" in table 1 indicates the following.

TMPTA: trimethylolpropane triacrylate (toagnosi co., ltd. Manufactured)

AD-TMP: di-trimethylolpropane tetraacrylate (Shin-Nakamura Chemical Co, manufactured by ltd.)

a-DCP: tricyclodecane dimethanol diacrylate (Shin-Nakamura Chemical Co, manufactured by ltd.)

EA-0250P:9, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene (Osaka Gas Chemicals co., ltd. & gt. Manufactured)

BR-113: dianal BR-113 (manufactured by Mitsubishi ray Co., ltd.)

BR95: dianal BR-95 (manufactured by Mitsubishi ray Co., ltd.)

Silplus HT100: silplus HT100 (Shin Nittetsu Sumikin Kabushiki kaisha manufactured)

Polysilazane: mixed solution of dibutyl ether solution of perhydro polysilazane (AQUAMICA NN120-20:AZ Electronic Materials Co, manufactured by ltd.) and dibutyl ether solution containing amine catalyst (N, N' -tetramethyl-1, 6-diaminohexane) (AQUAMICA NAX120-20:AZ Electronic Materials Co, manufactured by ltd.)

A9300: ethoxylated isocyanuric acid triacrylate (Shin-Nakamura Chemical Co, manufactured by Ltd.)

The "water content" in table 1 indicates the water content of the organic films (organic films 1 to 3) in each conductive laminate.

In the column "thin metal wire" in table 1, the case where the thin metal wire formed includes a MoNb film (blackened layer), a MoNb film (adhered layer), a Cu film (metal conductive layer), a CuNi film (adhered layer) and a MoNb film (protective layer) is denoted as "a", and the thin metal wire formed includes Mo ₂ N film (blackened layer), mo film (adhesive layer), al film (metal conductive layer), mo film (adhesive layer) and Mo ₂ The case of the N film (protective layer) is denoted as "B".

The "line width (μm)" of the thin metal line in table 1 indicates the line width of the thin metal line (line width on the 1 st organic film side of the blackened layer).

The "metal conductive layer thickness (nm)" in table 1 indicates the thickness of the metal conductive layer in the thin metal wire.

TABLE 1

As shown in table 1, the conductive laminate of the present invention exhibited the desired effect.

Among them, when the water content of the organic film was less than 1.00% (particularly, when 0.40% or less), it was confirmed that more excellent effects were exhibited.

Symbol description

10A, 10B, 10C-conductive laminate, 12-1 st organic film, 14A, 14B-fine metal wire, 16-2 nd organic film, 18-opening, 20-blackened layer, 22-adhesive layer, 24-conductive metal layer, 26-inorganic film, 28-support, 30-3 rd organic film, 40-grid pattern, 42-resistance value measuring terminal, 44-unit.

Claims

1. A conductive laminate, comprising:

a 1 st organic film;

An organic film 2 which is disposed so as to cover the thin metal wires,

the metal thin line comprises a blackening layer, an adhesion layer and a metal conducting layer from the 1 st organic film side in sequence,

the water content of the 1 st organic film and the 2 nd organic film is less than 3.00%,

the material constituting the 1 st organic film is acrylic resin, methacrylic resin or silicon-containing resin.

2. The conductive laminate according to claim 1, wherein,

the water content is less than 1.00%.

3. The conductive laminate according to claim 1 or 2, wherein,

the blackened layer and the adhesion layer contain the same metal atoms.

4. The conductive laminate according to claim 1 or 2, wherein,

the 1 st organic film and the 2 nd organic film are composed of the same material.

5. The conductive laminate according to claim 1 or 2, wherein,

the line width of the thin metal line gradually decreases from the 1 st organic film side toward the 2 nd organic film side.

6. The conductive laminate according to claim 1 or 2, wherein,

an inorganic film is disposed between the fine metal wire and the 2 nd organic film so as to cover the fine metal wire, the inorganic film including: at least one metal atom selected from the group consisting of Si, al and Ti.

7. The conductive laminate according to claim 6, wherein,

the inorganic film comprises: selected from the group consisting of SiO ₂ 、SiON、SiN、Al ₂ O ₃ TiO (titanium dioxide) ₂ At least one of the group of (c).

8. The conductive laminate according to claim 1 or 2, wherein,

the metal conductive layer comprises: at least one metal atom selected from the group consisting of Cu, al and Ag.

9. The conductive laminate according to claim 1 or 2, wherein,

The blackened layer comprises: at least one metal atom selected from the group consisting of Mo, nb, cr, ti and W.

10. The conductive laminate according to claim 1 or 2, wherein,

the conductive laminate further includes a support on the opposite side of the 1 st organic film from the 2 nd organic film side.

11. The conductive laminate according to claim 10, wherein,

the support body is a glass substrate.

12. The conductive laminate according to claim 1 or 2, wherein,

the 1 st organic film comprises a silicon-containing resin.

13. The conductive laminate according to claim 1 or 2, wherein,

the blackened layer comprises: at least one metal atom selected from the group consisting of Nb and W.

14. A touch panel comprising the conductive laminate of any one of claims 1 to 13.

15. A method for producing a conductive laminate, comprising:

a step of forming a 1 st organic film;

A step of forming a 2 nd organic film so as to cover the thin metal wires,

the metal thin wire comprises a blackening layer, an adhesion layer and a metal conducting layer from the 1 st organic film side in sequence, the water content of the 1 st organic film and the 2 nd organic film is less than 3.00%,